Alloyed zeolite catalyst component, method for making and catalytic application thereof

ABSTRACT

The presently disclosed and claimed inventive concept(s) generally relates to a method of making a solid catalyst component comprising a zeolite with a modifier and at least one Group VIII metal alloyed with at least one transition metal and a process of converting mixed waste plastics into low molecular weight organic compounds using the solid catalyst component. The process of converting mixed waste plastics into low molecular weight organic compounds may employ the use of a non-thermal catalytic plasma reactor, which may be configured as a fluid bed reactor or fixed bed reactor.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is continuation-in-part of U.S. Ser. No.16/270,436, filed Feb. 7, 2019, which is now U.S. Pat. No. 10,421,062,with an issue date of Sep. 24, 2019; which is a continuation of U.S.Ser. No. 15/194,857, filed Jun. 28, 2016, which is now U.S. Pat. No.10,239,049, issued on Mar. 26, 2019; which is a continuation of U.S.Ser. No. 13/396,160, filed Feb. 14, 2012, which is now U.S. Pat. No.9,404,045, issued on Aug. 2, 2016; which claims the benefit under 35U.S.C. 119(e) of U.S. Provisional Application Ser. No. 61/443,850, filedFeb. 17, 2011, the entirety of which is hereby expressly incorporatedherein by reference.

TECHNICAL FIELD

The presently disclosed and claimed inventive concept(s) generallyrelates to a solid catalyst component comprising a zeolite with amodifier and at least one Group VIII metal alloyed with at least onetransition metal. The presently disclosed and claimed inventiveconcept(s) further relates to a method of making the solid catalystcomponent and a process of converting mixed waste plastics into lowmolecular weight organic compounds using the solid catalyst component.

BACKGROUND OF THE INVENTION

In view of the increasing importance of polymers as substitutes forconventional materials of construction such as glass, metal, paper, andwood, the perceived need to convert non-renewable resources such aspetroleum and dwindling amount of landfill capacity available for thedisposal of waste products, considerable attention has been devoted inrecent years to the problem of recovering, reclaiming, recycling or insome way reusing mixed waste plastics.

It has been proposed to pyrolyze or catalytically crack the mixed wasteplastics so as to convert high molecular weight polymers into volatilecompounds having much lower molecular weight. The volatile compounds,depending on the process employed, can be either relatively high boilingliquid hydrocarbons useful as fuel oils or fuel oil supplements or lightto medium boiling hydrocarbons useful as gasoline-type fuels or aschemical “building blocks”.

U.S. Pat. No. 5,462,971 teaches a process for reclaiming a polyetherpolyol, comprising the steps of: (a) heating the polyether polyol and azeolite-containing particulate catalyst in a fluidized bed reaction zoneat a temperature effective to produce a volatile organic component and aspent catalyst component having carbon deposited thereon; (b)withdrawing a first stream comprising the volatile organic componentfrom the reaction zone; (c) withdrawing a second stream comprising thespent catalyst component; and (d) heating the second stream in aregeneration zone in the presence of oxygen at a temperature effectiveto convert the carbon to carbon dioxide and water and to regenerate thecatalyst.

It has also been proposed to pyrolyze or catalytically crack thermosetpolymers so as to convert the high molecular weight polymers intovolatile compounds having much lower molecular weight. U.S. Pat. No.5,192,809 teaches a process for reclaiming a filled thermoset polymer,comprising the steps of: (a) heating particles of the polymer and azeolite-containing particulate catalyst in a fluidized bed reaction zoneat a temperature effective to produce a coarse filler component, coke, avolatile organic component, and a spent catalyst component; (b)withdrawing a first stream comprising the volatile organic componentfrom the reaction zone; (c) withdrawing a second stream comprising thespent catalyst, the coke, and the coarse filler component from thereaction zone; (d) heating the second stream in a regeneration zone inthe presence of oxygen at a temperature effective to convert the coke tocarbon dioxide and water and to regenerate the catalyst; and (e)separating the regenerated catalyst and the coarse filler component.

It has been demonstrated that the pyrolysis of polyvinyl chloride (PVC)and polyvinylidene chloride (PVDC) can be performed in a two-steptemperature program to minimize the formation of chlorinatedhydrocarbons. The two-step temperature program eliminated the hydrogenchloride form the reactor and avoided the formation of chlorinatedhydrocarbons in the liquid products. The two-step pyrolysis produced theplastic derived oils without halogenated hydrocarbons (less than 15ppm). This work was published by Bhaskar, et al., in Green Chem., 2006,8, 697-700.

U.S. Pat. No. 5,079,385 teaches a process for converting solid plasticmaterials into usable lower molecular weight hydrocarbonaceous materialsby heating such plastic materials at elevated temperatures in effectivecontact with an acidic catalyst comprising at least one zeolite havingacid activity. The catalyst may be comprised of ZSM-5 and at least onecatalytic metal. The metal may be at least one of platinum, palladium,nickel, cobalt, iron, zinc, magnesium, molybdenum, tungsten, titanium,gallium, tantalum and chromium. The process claims co-feeding ofhydrogen or a source of hydrogen to the reaction zone.

SUMMARY OF THE INVENTION

The following presents a simplified summary of the presently disclosedand claimed inventive concept(s) in order to provide a basicunderstanding of some aspects of the presently disclosed and claimedinventive concept(s). This summary is not an extensive overview of thepresently disclosed and claimed inventive concept(s). It is intended toneither identify key or critical elements of the presently disclosed andclaimed inventive concept(s) nor delineate the scope of the presentlydisclosed and claimed inventive concept(s). Rather, the sole purpose ofthis summary is to present some concepts of the presently disclosed andclaimed invention in a simplified form as a prelude to the more detaileddescription that is presented hereafter.

The presently disclosed and claimed inventive concept(s) provides asolid catalyst component, a method of making the solid catalystcomponent and a process of converting mixed waste plastics into lowmolecular weight organic compounds using the solid catalyst component.The solid catalyst component comprises a zeolite with a modifier and atleast one Group VIII metal alloyed with at least one transition metal.The modifier can be phosphorus, boron, an additive, or combinationsthereof. The additive can be gallium, zinc, zirconium, niobium,tantalum, or combinations thereof. The Group VIII metals can beplatinum, palladium, silver, gold, rhodium, ruthenium, iridium orcombinations thereof. The transition metals can be titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum,tungsten or combinations thereof.

The mixed waste plastics can be converted into lower molecular weightorganic compounds used as chemical intermediates, solvents, or fuels.The fillers such as glass fibers or inorganic powders can be recoveredin re-useable form from the mixed waste plastics. PVC, PVDC and otherhalogenated plastics can be decomposed in a pre-pyrolysis step. Thepresently disclosed and claimed inventive concept(s) pertains to the useof a fluid-bed reactor or a fixed bed reactor and an integrated catalystregenerator for continuous catalyst recycling operation. Hydrogen and/ora hydrogen source such as methanol can be added to the mixed wasteplastic feed. In addition, lights, gases and olefins generated can berecycled back to the reactor.

To the accomplishment of the foregoing and related ends, the presentlydisclosed and claimed inventive concept(s) involves the featureshereinafter fully described and particularly pointed out in the claims.The following description and the annexed drawing set forth in detailcertain illustrative aspects and implementations of presently disclosedand claimed inventive concept(s). These are indicative, however, of buta few of the various ways in which the principles of the presentlydisclosed and claimed inventive concept(s) may be employed. Otherobjects, advantages and novel features of the presently disclosed andclaimed inventive concept(s) will become apparent from the followingdetailed description of the presently disclosed and claimed inventiveconcept(s) when considered in conjunction with the drawing.

BRIEF SUMMARY OF THE DRAWING

FIG. 1 is a high level schematic diagram of a process for convertingmixed waste plastics into low molecular weight organic compounds.

DETAILED DESCRIPTION

The presently disclosed and claimed inventive concept(s) generallyrelates to a solid catalyst component comprising a zeolite with amodifier and at least one Group VIII metal alloyed with at least onetransition metal, a method of making the solid catalyst component, and aprocess of converting mixed waste plastics into low molecular weightorganic compounds using the solid catalyst component.

In this context, the term “zeolite” encompasses not only the truezeolites, which are characterized by having crystalline aluminosilicatethree-dimensional structures arising from a framework of [SiO₄]⁴⁻ and[AlO₄]⁵⁻ coordination polyhedra linked through their corners, but alsothe “zeotypes”, which are crystalline silicates that resemble truezeolites in structure and properties but are essentially alumina-free.

Zeotypes are exemplified by crystalline silica polymorphs (e.g.,silicates, disclosed in U.S. Pat. No. 4,061,724 and organosilicates,disclosed in U.S. Pat. No. Re. 29,948), chromia silicates (e.g., CZM),ferrosilicates and galliosilicates (disclosed in U.S. Pat. No.4,238,318), and borosilicates (disclosed U.S. Pat. Nos. 4,226,420,4,269,813, and 4,327,236).

The use of crystalline aluminosilicate zeolite is preferred, however,such zeolites are well known and are described in Szostak, MolecularSieves: Principles of Synthesis and Identification, Van NostrandReinhold (1989); Dyer, An Introduction to Zeolite Molecular, SievesWiley (1988); Jacobs, Carboniogenic Activity of Zeolite, Elseviar(1977); Breck, Zeolite Molecular Sieves: Structure, Chemistry, and Use,Wiley (1974); and Breck et al. “Molecular Sieves”, in Kirk-OthmerEncyclopedia of Chemical Technology Vol. 15, p. 638.

Without limitation, zeolites can be selected from naturally-occurringzeolites, synthetic zeolites and combinations thereof. In certainembodiments, the zeolite can be a Mordenite Framework Inverted (MFI)type zeolite, such as a ZSM-5. Optionally, such a zeolite can compriseacidic sites.

In general, the ZSM-5 is ordinarily ion exchanged with a desired cationto replace alkali metal present in the zeolite as prepared. The exchangetreatment is such as to reduce the alkali metal content of the finalcatalyst to less than about 0.5 weight percent, and preferably less thanabout 0.1 weight percent. The preferred proton source is ammoniumchloride as opposed to hydrochloric acid, sulfuric acid and nitric acid.Ion exchange is suitably accomplished by conventional contact of thezeolite with an aqueous solution of the proton source.

Other types of zeolites include, but are not limited to, ferrierite,zeolite L, zeolite boron beta, TEA-modernite, ITQ-1, ITQ-21, MCM-22,MCM-36, MCM-39, MCM-41, MCM-48, PSH-3, Breck-6, ZSM-4, ZSM-8, ZSM-11,ZSM-12, ZSM-20, ZSM-21, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48,ZSM-50, ZSM-57, SUZ-4, EU-1, SAPO-5, SAPO-11, SAPO-34, (S)AIPO-31,SSZ-23, TUD-1, VPI-5, and the like.

It will also be desirable to utilize the acidic forms of zeolites suchas the ZSM types and borosilicates. HZSM-5 is particularly useful.

Other representative zeolites suitable for use include, but are notlimited to, zeolite A (U.S. Pat. No. 2,882,243), zeolite X (U.S. Pat.No. 2,882,244), zeolite Y (U.S. Pat. No. 3,130,007), zeolite ZK-5 (U.S.Pat. No. 3,314,752), mordenite, chabazite, faujasite, erionite,offretite, and zeolite beta. Mixtures of zeolites may also be employed.

Also suitable for use will be zeolites loaded or doped with Group VIIImetals such as platinum and palladium to facilitate secondary functionssuch as hydrogenation or hydrogenolysis in addition to the basiccracking reaction. Such bifunctional zeolites are well known and aredescribed, for example, in Chapter V of Jacobs, Carboniogenic Activityof Zeolites, Elsever (1977).

The pore size of the zeolite can be varied to control the composition ofthe volatile organic component produced by reacting with mixed wasteplastics. Thus, the pore size may be small (a pore/channel diameter <5angstroms; generally, those zeolites having 8 tetrahedra constitutingtheir pore defining ring), intermediate (a pore/channel diameter between5-7 angstroms; generally, those zeolites having 10 tetrahedra or 12puckered tetrahedra constituting their pore defining ring), or large (apore/channel diameter >7 angstroms; generally, those zeolites havingmore than 12 tetrahedra in their pore defining ring). In general, theuse of large pore size zeolite favors the production of higher molecularweight and higher boiling volatile organic compounds from the mixedwaste plastics.

It may be desirable, in some embodiments, to employ one or more zeolitesto establish a bimodal distribution of pore sizes. In some cases, asingle zeolite with a bimodal distribution of pore sizes may be used(e.g., a single zeolite that contains predominantly 5.9-6.3 Å pores and7-8 Å pores). In other cases, a mixture of two or more zeolites can beemployed to establish the bimodal distribution (e.g., a mixture of twozeolites, each zeolite including a distinct range of average poresizes).

For example, in some embodiments at least about 70%, at least about 80%,at least about 90%, at least about 95%, at least about 98%, or at leastabout 99% of the pores of the one or more zeolites have smallestcross-sectional diameters that lie within a first size distribution or asecond size distribution. In some cases, at least about 2%, at leastabout 5%, or at least about 10% of the pores of the one or more zeoliteshave smallest cross-sectional diameters that lie within the first sizedistribution; and at least about 2%, at least about 5%, or at leastabout 10% of the pores of the one or more catalysts have smallestcross-sectional diameters that lie within the second size distribution.In some cases, the first and second size distributions are selected fromthe ranges provided above. In certain embodiments, the first and secondsize distributions are different from each other and do not overlap. Anexample of a non-overlapping range is 5.9-6.3 Angstroms and 6.9-8.0Angstroms, and an example of an overlapping range is 5.9-6.3 Angstromsand 6.1-6.5 Angstroms. The first and second size distributions may beselected such that the ranges are not immediately adjacent one another,an example being pore sizes of 5.9-6.3 Angstroms and 6.9-8.0 Angstroms.An example of a range that is immediately adjacent one another is poresizes of 5.9-6.3 Angstroms and 6.3-6.7 Angstroms.

As a specific example, in some embodiments one or more zeolites are usedto provide a bimodal pore size distribution for the simultaneousproduction of aromatic and olefin compounds. One pore size distributionmay advantageously produce a relatively high amount of aromaticcompounds, and the other pore size distribution may advantageouslyproduce a relatively high amount of olefin compounds. In someembodiments, at least about 70%, at least about 80%, at least about 90%,at least about 95%, at least about 98%, or at least about 99% of thepores of the one or more zeolites have smallest cross-sectionaldiameters between about 5.9 Angstroms and about 6.3 Angstroms or betweenabout 7 Angstroms and about 8 Angstroms. In addition, at least about 2%,at least about 5%, or at least about 10% of the pores of the one or morecatalysts have smallest cross-sectional diameters between about 5.9Angstroms and about 6.3 Angstroms; and at least about 2%, at least about5%, or at least about 10% of the pores of the one or more catalysts havesmallest cross-sectional diameters between about 7 Angstroms and about 8Angstroms.

In some embodiments, at least about 70%, at least about 80%, at leastabout 90%, at least about 95%, at least about 98%, or at least about 99%of the pores of the one or more zeolites have smallest cross-sectionaldiameters between about 5.9 Angstroms and about 6.3 Angstroms or betweenabout 7 Angstroms and about 200 Angstroms. In addition, at least about2%, at least about 5%, or at least about 10% of the pores of the one ormore zeolites have smallest cross-sectional diameters between about 5.9Angstroms and about 6.3 Angstroms; and at least about 2%, at least about5%, or at least about 10% of the pores of the one or more zeolites havesmallest cross-sectional diameters between about 7 Angstroms and about200 Angstroms.

In some embodiments, at least about 70%, at least about 80%, at leastabout 90%, at least about 95%, at least about 98%, or at least about 99%of the pores of the one or more zeolites have smallest cross-sectionaldiameters that lie within a first distribution and a seconddistribution, wherein the first distribution is between about 5.9Angstroms and about 6.3 Angstroms and the second distribution isdifferent from and does not overlap with the first distribution. In someembodiments, the second pore size distribution may be between about 7Angstroms and about 200 Angstroms, between about 7 Angstroms and about100 Angstroms, between about 7 Angstroms and about 50 Angstroms, orbetween about 100 Angstroms and about 200 Angstroms. In someembodiments, the second zeolite may be mesoporous (e.g., having a poresize distribution of between about 2 nm and about 50 nm).

The solid catalyst component of this presently disclosed and claimedinventive concept(s) comprises either an unbound (unsupported) zeolite,or a zeolite combined with a binder (co-gel) or a support. Such zeolitebinders or supports are well known in the art, as are methods ofpreparing bound or supported zeolites. Specific examples of the bindersinclude, but are not limited to, silica, alumina, silica-alumina,silica-titania, silica-thoria, silica-magnesia, silica-zirconia,silica-beryllia, and ternary compositions of silica with otherrefractory oxides. Other useful binders or supports are clays such asmontmorillonites, kaolins, bentonites, halloysites, dickites, nacritesand anaxites.

If a binder is used, it can be combined with a zeolite before or afterthe process by which metals are incorporated into the zeolite. Thebinder can comprise between about 2% and about 98% by weight of thecombined weight of the binder and the zeolite. The quantity of thebinder in the solid catalyst component is selected to achieve desiredcrush strength while maintaining sufficient catalyst activity in view ofthe dilution of the zeolite by the binder. In one embodiment, the bindercomprises between about 5% by weight and about 70% by weight of thecombined weight of the binder and the zeolite. In another embodiment,the binder comprises between about 10% by weight and about 50% by weightof the combined weight of the binder and the zeolite. In yet anotherembodiment, the binder comprises between about 15% by weight and about30% by weight of the combined weight of the binder and the zeolite.

In the presently disclosed and claimed inventive concept(s), the zeolitecan be modified by phosphorus, boron, and/or an additive. Zeolitescontaining group VA elements, especially phosphorus-containing zeolites,are particularly preferred for use since it has been unexpectedly foundthat this class of zeolites is very tolerant of steam and tends toretain an unusually high degree of activity and selectivity in thepresence of steam. Zeolites containing Group VA elements are describedin U.S. Pat. Nos. 3,977,832, 3,925,208, and 4,379,761, for example andin Vedrine, J. Catal. 73, 147 (1982).

Boron-containing zeolites or borosilicates (as described in U.S. Pat.Nos. 3,328,119, 4,029,716, 4,078,009, 4,269,813 and 4,656,016; andEuropean Pat Pub. Nos. 77,946 and 73,482) are also especially preferredfor use in view of the finding that such zeolites similarly showextremely good steam tolerance.

In general, the zeolite containing phosphorus, boron, or phosphorus andboron has a surface Si/Al ratio in the range from about 20 to about 60.Phosphorus, boron, or phosphorus and boron can be added to a zeolite byimpregnating the zeolite with phosphorus, boron, or phosphorus and boroncompound(s) in accordance with the procedures described, for example, inU.S. Pat. No. 3,972,832. In anther embodiment, the phosphorus, boron, orphosphorus and boron compound(s) can be added to multicomponent mixturesfrom which the solid catalyst component is formed. The phosphorus,boron, or phosphorus and boron compound(s) is added in amountssufficient to provide a final zeolite composition having about 0.1 toabout 10 wt. % phosphorus, boron, or phosphorus and boron. In oneembodiment, the zeolite contains about 1 to about 3 wt. % of phosphorus,boron, or phosphorus and boron.

In an additional embodiment, the zeolite is activated with steam afterincorporation of phosphorus, boron, or phosphorus and boron therein. Thesteam treatment may be in a preferred embodiment carried out as adiscrete step prior to use of the catalyst. In one embodiment, thezeolite is heated at a temperature from about 500° C. to about 700° C.under about 1 to about 5 atmospheres steam for about 1 to about 48hours. In another embodiment, the zeolite is heated at a temperaturefrom about 550° C. to about 600° C. under about 1.5 to about 3atmospheres steam for about 15 to about 30 hours.

An alternative method is to add about 1 to about 50 mol. % steam basedon the total moles of the mixed waste plastic feed during the conversionprocess. In one embodiment about 2 to about 20 mol. % steam based on thetotal moles of the mixed waste plastic feed can be used to obtainfurther improvements in activity.

The additive may comprise a metal and/or a metal oxide. Specificexamples of metals and/or oxides include, but are not limited to,gallium, zinc, zirconium, niobium, tantalum, and any of their oxides.The additives may be in the form of readily available compounds such asthe metal salts with counter-anions such as nitrates, acetates, halides,oxy-halides, sulfates and the like.

In one embodiment, the metal and/or metal oxide can be impregnated intothe zeolite (e.g., in the interstices of the lattice structure of thezeolite). In another embodiment, the metal and/or metal oxide can beincorporated into the lattice structure of the zeolite. For example, themetal and/or metal oxide might be included during the preparation of thezeolite, and the metal and/or metal oxide can occupy a lattice site ofthe resulting zeolite. The metal and/or metal oxide can react orotherwise interact with a zeolite such that the metal and/or metal oxidedisplaces an atom within the lattice structure of the zeolite. In yetanother embodiment, metal and/or metal oxide can partially beincorporated into the lattice structure of the zeolite during thepreparation of the zeolite and partially be impregnated into thezeolite.

In certain embodiments, a Mordenite Framework Inverted (MFI) zeolitecomprising gallium, such as a galloaluminosilicate MFI (GaAlMFl)zeolite, can be used. GaAlMFl zeolite can be formed by replacing some ofthe Al atoms of aluminosilicate MFI zeolite with Ga atoms. In someinstances, the zeolite can be in the hydrogen form (e.g., H—GaAlMFl).The galloaluminosilicate MFI zeolite can be a ZSM-5 in which some of thealuminum atoms have been replaced with gallium atoms.

In one embodiment, the ratio of moles of Si in the galloaluminosilicatezeolite to the sum of the moles of Ga and Al (i.e., the molar ratioexpressed as Si:(Ga+Al)) in the galloaluminosilicate zeolite can be atleast about 15:1, at least about 20:1, at least about 25:1, at leastabout 35:1, at least about 50:1, at least about 75:1, or higher. Inanother embodiment, it is advantageous to employ a zeolite with a ratioof moles of Si to the sum of the moles of Ga and Al of from about 15:1to about 100:1, from about 15:1 to about 75:1, from about 25:1 to about80:1, or from about 50:1 to about 75:1

In one embodiment, the ratio of moles of Si to the moles of Ga in thegalloaluminosilicate zeolite can be at least about 30:1, at least about60:1, at least about 120:1, at least about 200:1. In another embodiment,the ratio of moles of Si to the moles of Ga in the galloaluminosilicatezeolite can be varied from about 30:1 to about 300:1, from about 30:1 toabout 200:1, from about 30:1 to about 120:1, or from about 30:1 to about75:1.

In one embodiment, the ratio of the moles of Si to the moles of Al inthe galloaluminosilicate zeolite can be at least about 10:1, at leastabout 20:1, at least about 30:1, at least about 40:1, at least about50:1, at least about 75:1. In another embodiment, the ratio of the molesof Si to the moles of Al in the galloaluminosilicate zeolite can bevaried from about 10:1 to about 100:1, from about 10:1 to about 75:1,from about 10:1 to about 50:1, from about 10:1 to about 40:1, or fromabout 10:1 to about 30:1.

The modifiers can be added to the zeolite by known methods in the artincluding incipient wetness impregnation; wet impregnation; depositionmethods including physical, chemical, vapor and atomic deposition means;and other synthetic means well known in the art.

In addition to the zeolite with the modifier(s), the solid catalystcomponent also contains at least one Group VIII metal alloyed with atleast one transition metal. Alloyed metals are commonly referred to asbimetallic or multimetallic materials (surfaces). A catalyst containingalloyed metals often shows electronic and chemical properties that aredistinctly different from those of the parent metals. The catalyst showsenhanced selectivity, activity and stability. Generally, it is believedthat two factors, contribute to the modification of the electronic andchemical properties of a metal in a bimetallic or multimetallic material(surface). First, the formation of the hetero-atom bonds changes theelectronic environment of the metal surface, giving rise tomodifications of its electronic structure through the ligand effect.Second, the geometry of the bimetallic or multimetallic material(surface) is typically different from that of the parent metals, e.g.the average metal-metal bond lengths change. This gives rise to thestrain effect that is known to modify the electronic structure of themetal through changes in orbital overlap.

Specific examples of the Group VIII metals include, but are not limitedto, platinum, palladium, silver, gold, rhodium, ruthenium, and iridium.The Group VIII metal can be added to the zeolite such as the spray driedmaterial and/or support by known methods in the art including incipientwetness impregnation; wet impregnation; deposition methods includingphysical, chemical, vapor and atomic deposition means; and othersynthetic means well known in the art. The Group VIII metal may be inthe form of readily available compounds such as the metal salts withcounter-anions such as nitrates, acetates, halides, oxy-halides,sulfates, nitrides, sulfides and the like.

Specific examples of the transition metals include, but are not limitedto, titanium, vanadium, chromium, manganese, iron, cobalt, nickel,copper, zinc, molybdenum, and tungsten. The transition metal may beadded to the zeolite such as the spray dried material and/or support byknow methods in the art including incipient wetness impregnation; wetimpregnation; deposition methods including physical, chemical, vapor andatomic deposition means; and other synthetic means well know in the art.The transition metal may be in the form of readily available compoundssuch as the metal salts with counter-anions such as nitrates, acetates,halides, oxy-halides, sulfates nitrides, sulfides and the like.

In one embodiment, the solid catalyst components include Pt, Pd, or Ptand Pd as one of the Group VIII metals; and Ni, Co, or Ni and Co as oneof the transition metals. Specific examples include PtNi, PtCo, PtNiCo,PdNi, PdCo, PtNiCo, PtPdNi, PtPdCo and PtPdNiCo.

A lattice constant can be calculated from 2 θ of a Group VIII/Transitionmetal alloy peak observed in an X-ray diffraction (XRD) pattern of analloy metal prepared using an arc-melting method (Gasteiger, H. A. etal., LEIS and AES on sputtered and annealed polycrystalline GroupVIII/Transition metal bulk alloys, Surface Science, 293 (1993), pp.67-80). Also, a method of calculating an alloy ratio of Group VIII metaland transition metal from the lattice constant is disclosed in the aboveliterature.

Based on this method, an alloy ratio of Group VIII metal and transitionmetal is calculated in the present application. In order to maximize themultimetallic effects, it is advantageous that the Group VIII metal atomcorresponds to the transition metal atom in a ratio from about 10:1 toabout 1:10. In one embodiment, the ratio of Group VIII metal totransition metal can be changed from about 5:1 to about 1:5. In anotherembodiment, the ratio of Group VIII metal to transition metal can bechanged from about 3:1 to about 1:3.

In general, the solid catalyst component contains from about 0.01 weight% to about 2.0 weight % of the multimetallic (e.g. bimetallic ortrimetallic) component. In one embodiment, the solid catalyst componentcontains from about 0.02 weight % to about 1.0 weight % of themultimetallic component. In another embodiment, the solid catalystcomponent contains from about 0.05 weight % to about 0.5 weight % of themultimetallic component.

These multimetallic components can be incorporated with the zeolite byany of the conventional techniques known for this purpose, such as wetimpregnation, incipient wetness impregnation, ion exchange, frameworksubstitution, physical vapor deposition, chemical vapor deposition,atomic layer deposition, or physical bending.

In one embodiment, multimetallic component incorporation is by ionexchange. Because the zeolites are highly selective, a salt of themultimetallic component can be chosen to enhance uptake of themultimetallic component. For example, tetraammine salts (e.g. chlorides,nitrates or hydroxides) of the multimetallic component can be preparedand used to incorporate the multimetallic component into the zeolite.The multimetallic component may also be incorporated using a sequentialprocess, sometimes referred to as “double dip”, in which the zeolite isexposed to the salt solution, followed by drying and calcining to fixthe multimetallic component in the zeolite, and the process is repeateduntil the desired amount of the multimetallic component has beenincorporated into the zeolite.

In general, the solid catalyst component has an extrudate diameter ofbetween about 0.08 mm and about 2.5 mm. When used in a fixed-bed reactorthe extrudate diameter can be at least about 0.5 mm with an upper limitof about 1.8 mm. The catalyst has an average micropore diameter of about7.4 Å when using zeolite X or Y.

The particle size of the solid catalyst component may be smaller in afluidized bed reactor such that the catalyst component may be readilyfluidized in the reactor. In general, the solid catalyst componentshould have a particle size from about 10 to about 150 microns. Tofacilitate the separation of the catalyst component from the fillercomponent of a filled mixed waste plastic, it will be advantageous toselect a solid catalyst component which is relatively uniform inparticle size (i.e., one that does not have a high proportion ofparticles that are substantially different in size from the averageparticle size).

A method of preparing a solid catalyst component comprising a modifiedzeolite and a Group VIII/Transition metal alloy according to anembodiment of the presently disclosed and claimed inventive concept(s)will now be described.

First, a Group VIII metal precursor and a transition metal precursor aredissolved in a solvent such as water, respectively. The Group VIII metalprecursor and the transition metal precursor can be in the form of saltscapable of being easily dissociated in water, for example, chlorides,sulfides, nitrides of Group VIII metal and transition metal,respectively.

The Group VIII metal precursor and the transition metal precursor can beweighed such that a molar ratio of the Group VIII metal precursor andthe transition metal precursor is from about 10:1 to about 1:10. If themolar ratio of the Group VIII metal precursor and the transition metalprecursor deviates from the above range, a molar ratio of the Group VIIImetal and transition metal in the Group VIII/Transition Metal alloycatalyst component to be formed may be also deviated from a range ofabout 10:1-1:10 in many cases. In one embodiment, the Group VIII metalprecursor and the transition metal precursor can be weighed such that amolar ratio of the Group VIII metal precursor and the transition metalprecursor is from about 5:1 to about 1:5. In another embodiment, theGroup VIII metal precursor and the transition metal precursor can beweighed such that a molar ratio of the Group VIII metal precursor andthe transition metal precursor is from about 3:1 to about 1:3. The waterused can be deionized water.

Next, the solution of the Group VIII metal precursor in water is mixedwith the solution of the transition metal precursor in water to obtain ametal salt solution.

A modified zeolite for supporting the active components of Group VIIImetal and transition metal is dispersed in a solvent to obtain a zeoliteslurry. The modified zeolite can be prepared by incorporating a modifierinto a zeolite. The modifier is phosphorus, boron, or phosphorus andboron. An additive can also be added as a modifier in addition tophosphorus, boron, or phosphorus and boron. The additive is selectedfrom the group consisting of gallium, zinc, zirconium, niobium, tantalumand combinations thereof. The modifier can be incorporated into thezeolite by any suitable method or means known in the art forincorporating elements into a substrate material.

The phosphorus, boron, and additive compounds can be incorporated intothe zeolite by individual incorporation steps by which the compounds areindividually and separately incorporated into the zeolite or by anycombination of simultaneous incorporation steps by which any two or moreof the compounds are incorporated into the zeolite.

In one embodiment, a single step method of incorporating the phosphorus,boron and additive into the zeolite is by using an aqueous impregnationsolution into which is dissolved suitable compounds containingphosphorus, boron, and the additive. This incorporation method morespecifically can be any standard incipient wetness technique known inthe art.

The solvent in which the modified zeolite to be dispersed may be anorganic solvent that can also function as a reducing agent. In oneembodiment, the solvent is an organic solvent containing a hydroxy (OH)group. In another embodiment, the solvent is an organic solventcontaining two or more OH groups. In yet another embodiment, the organicsolvent is ethylene glycol. A weight ratio of the organic solvent usedin the zeolite slurry and the water used in the metal salt solution maybe in the range from about 1:0.4 to about 1:0.6.

The metal salt solution is contacted with the zeolite slurry to obtain amixture, and then the pH of the mixture is adjusted to form a product.Thus, the active components are reduced during the reduction process,while being supported on the zeolite. The pH of the mixture can beadjusted to about 11-13 by using a pH adjusting agent. Specific examplesof the pH adjusting agents include, but are not limited to, NaOH, NH₄OH,KOH, Ca(OH)₂ or combinations thereof.

Subsequently, the product after the pH adjustment is slowly heated toform catalyst particles. The temperature is raised from room temperatureto a final temperature of about 50-80° C. for about 20-40 minutes andthen maintained at the final temperature for about 1-5 hours. The formedcatalyst particles are isolated using a conventional method, forexample, filtration or centrifuging, and then washed.

The catalyst particles can also be obtained in other alternative ways.For example, the solution of the Group VIII metal precursor in water iscontacted with the zeolite slurry to form a Group VIII metal zeliotemixture. A pH adjusting agent is added into the Group VIII metal zeolitemixture to form a Group VIII metal zeolite product. The pH adjustingagent can be the same as those described previously. Then the Group VIIImetal zeolite product is slowly heated to form a Group VIII metalzeolite catalyst precursor. The temperature is raised from roomtemperature to a final temperature of about 50-80° C. for about 20-40minutes and then maintained at the final temperature for about 1-5hours. The formed Group VIII metal zeolite catalyst precursor isisolated using a conventional method, for example, filtration orcentrifuging, and then washed. Next, the Group VIII metal zeolitecatalyst precursor is dried in air at a temperature of about 110° C.

Next, the dried Group VIII metal zeolite catalyst precursor is dispersedin a solvent to obtain Group VIII metal zeolite slurry. The solvent inwhich the Group VIII metal zeolite catalyst precursor to be dispersedmay be an organic solvent that can also function as a reducing agent.The solvent can be the same one used to form a zeolite slurry describedpreviously.

The solution of the transition metal precursor in water is contactedwith the Group VIII metal zeolite slurry to form a mixture. A pHadjusting agent is added into the mixture to form a product. The pHadjusting agent can be the same as those described previously.Subsequently, the product after the pH adjustment is slowly heated toform catalyst particles. The temperature is raised from room temperatureto a final temperature of about 50-80° C. for about 20-40 minutes andthen maintained at the final temperature for about 1-5 hours. The formedcatalyst particles are isolated using a conventional method, forexample, filtration or centrifuging, and then washed.

Similarly, the solution of the transition metal precursor in water iscontacted with the zeolite slurry to form a transition metal zeliotemixture. The pH adjusting agent is added into the transition metalzeolite mixture to form a transition metal zeolite product. Then thetransition metal zeolite product is slowly heated to form a transitionmetal zeolite catalyst precursor. The temperature is raised from roomtemperature to a final temperature of about 50-80° C. for about 20-40minutes and then maintained at the final temperature for about 1-5hours. The formed transition metal zeolite catalyst precursor isisolated using a conventional method, for example, filtration orcentrifuging, and then washed. Next, the transition metal zeolitecatalyst precursor is dried in air at a temperature about 110° C.

The transition metal zeolite catalyst precursor is dispersed in thesolvent to obtain transition metal zeolite slurry. The solution of theGroup VIII metal precursor in water is contacted with the transitionmetal zeolite slurry to form a mixture. The pH adjusting agent is addedinto the mixture to form a product. Subsequently, the product after thepH adjustment is slowly heated to form catalyst particles. Thetemperature is raised from room temperature to a final temperature ofabout 50-80° C. for about 20-40 minutes and then maintained at the finaltemperature for about 1-5 hours. The formed catalyst particles areisolated using a conventional method, for example, filtration orcentrifuging, and then washed.

Finally, the washed catalyst particles are heat-treated to prepare thesolid catalyst component. The heat-treatment has two steps. First, thecatalyst particles are dried in air at about 110° C. Second, the driedcatalyst particles are calcinated in air at a temperature in the rangefrom about 250 to about 500° C. In one embodiment, the dried catalystparticles can be calcinated at about 400° C. in air. This calcinationprocess results in the formation of the alloy in which the Group VIIImetal(s) and the transition metal(s) are intimately mixed at the atomiclevel so that there are no atomic clusters of one distinct Group VIIImetal or one distinct transition metal. At the atomic level a Group VIIImetal atom is always in close atomic proximity (nearest atomic neighbor)to a transition metal atom, continuously through-out the alloycomposition. The heat-treatment time may be varied from about 5 minutesto about 2 hours, depending on the amount of the catalyst to be formed.

The solid catalyst component can be used in different catalyticreactions. One specific example of using the solid catalyst component isto convert mixed waste plastics into low molecular weight organiccompounds. The mixed waste plastics used in the presently disclosed andclaimed inventive concept(s) can be selected from a wide range ofplastics and polymers including hydrocarbon and oxygenated hydrocarbonplastic resin materials, halogenated plastics, thermoset polymers,thermoplastic polymers, and combinations thereof.

The solid catalyst component has great utility with hydrocarbon polymersincluding, especially, polyolefins such as polyethylene, polypropylene,polybutene, and polymers and copolymers of these and other unsaturatedhydrocarbon monomers. Polyvinyl aromatics such as polystyrene e.g.foamed polystyrene, and poly (paramethyl-styrene) and copolymers e.g.with cross-linking comonomers such as divinylbenzene (DVB) can also berecovered using the solid catalyst component as oxygenated polymers suchas polyesters e.g. polyethylene terephthalate (PET), polyacrylates e.g.poly (methyl methacrylate), polycarbonates and other such polymers.

Any thermoset polymer can also be employed in the presently disclosedand claimed inventive concept(s), including not only polymers which arealready crosslinked but also thermosettable or partially thermosetmaterials which would ordinarily be subject to crosslinking uponheating. A thermoset polymer in this context thus means a polymer whichcannot be remelted or remolded without destroying its originalcharacteristics, or a polymer subject to crosslinking reactions attemperatures necessary to induce flow. Examples of suitable thermosetresins include, but are not limited to, epoxy resins, melamine resins,phenolic resins (e.g., phenol-formaldehyde resins), urea resins, aminoresins, unsaturated polyester resins, melamine-formaldehyde resins,allylic resins, thermoset polyimides, as well as mixtures thereof.

Thermoset polymers derived from an isocyanate-containing reactant areparticularly advantageous for use, as the process of this presentlydisclosed and claimed inventive concept(s) enables the preparation ofmonomeric or oligomeric organic amines from such polymers in relativelyhigh yield. Amines have high value as chemical intermediates and may beused to prepare isocyanates, amides, amine salts, azo compounds, ureas,carbamates, and other useful types of compounds. This result wasunexpected, since the catalytic cracking of polymeric materials hasheretofore given predominantly hydrocarbons (i.e., compound containingonly carbon and hydrogen) and since difficulties with catalystdeactivation or undesired side reactions are commonly encountered whenheteroatom-containing substrates are employed. Illustrative thermosetpolymers derived from isocyanate-containing reactants include, forexample, polyurethanes (polymers obtained by reacting di- orpolyisocyanates with hydroxy-containing reactants such as polyetherpolyols, polyester polyols, glycols, and the like), polyureas (polymersobtained by reacting di- or polyisocyanates with amine-containingreactants such as amine-tipped polyether polyols, amine chain extendersor curatives, and the like), polyisocyanurates (polymers obtained bytrimerization of an isocyanate), as well as hybrid or mixed typethermoset resins such as polyurethane-modified polyisocyanurates(polymers obtained by reacting a portion of the isocyanate groups of adi- or polyisocyanate with an hydroxy-containing reactant andtrimerizing another portion of the isocyanate groups). Polymers of thelatter type are well-known and are described, for example, in U.S. Pat.Nos. 4,965,038, 4,731,427, and 5,059,670. The thermoset polymers derivedfrom isocyanate-containing reactants may be in various forms such asflexible foams, rigid foams, microcellular elastomers, coatings,adhesives, sealants, and solid elastomers.

A distinct advantage of the presently disclosed and claimed inventiveconcept(s) is that mixtures of various thermoset polymers can beutilized as the feed. Another advantage of the presently disclosed andclaimed inventive concept(s) is that thermoplastic polymers such aspolyethylene, polypropylene, polystyrene, polyamide (nylon), polyvinylchloride, polyethylene terephthalate, polybutylene terephthalate,polymethyl methacrylate, polyphenylene oxide, styrene/maleic anhydridecopolymer, ABS and MBS resins, thermoplastic polyurethanes, andelastomers and rubbers such as natural rubbers, polybutadiene,polyolefin rubbers, butyl rubbers, neoprenes, polyisobutylene, silicoanerubbers, nitrile rubbers, styrene-butadiene or styrene-isoprene rubbersand acrylate rubbers can also be employed as admixtures with thethermoset polymer, since such thermoplastics and rubbers will besuccessfully cracked or converted to useful volatile organic compoundssimultaneous with transformation of the thermoset polymer. Moreover,cellulose-based organic wastes such as paper or wood will not adverselyaffect the process of this presently disclosed and claimed inventiveconcept(s). Thus, the need for tedious and expensive separation stepsprior to introduction of the raw material feed into the reactor isminimized.

Another advantage of the process of this presently disclosed and claimedinventive concept(s) is the ability to handle a feed stream containinghighly filled thermoset polymers, since the filler or reinforcement inthe feed stream is effectively separated from the volatile organicproducts derived from the polymer and recovered in a form whereby it maybe subsequently reused as a filler to improve the physical andmechanical properties of virgin polymers. Surprisingly, the presence ofthe filler in the process does not adversely affect the yields ofvolatile organic compounds obtainable in the process or affect theactivity of the solid catalyst component. Typically, a filled thermosetpolymer will contain up to about 50 or to about 75% by weight of one ormore fillers. The fillers may be any of the conventional additivesincorporated into thermoset resin, including, for example, glass fibers(strands, filament yarns, staple fibers, staple yarns, woven or unwovenmats, long or short fibers), glass flakes, glass spheres, asbestos,calcium carbonates, dolomite, silicates, talc, kaolin, mica, feldspar,silicas, wollastonite, barium sulfate, alumina, and other mineral orinorganic fillers and reinforcements. Thermoset polymers containingcarbon-based fillers and reinforcements such as carbon black, carbonfibers, graphite, synthetic reinforcing fibers such as aromatic amidepolymers (e.g., “KEVLAR®”, a product of E. I. du Pont de Nemours) canalso be readily processed and reclaimed by the process of this presentlydisclosed and claimed inventive concept(s).

The process of this presently disclosed and claimed inventive concept(s)is especially useful for processing the “fluff” obtainable from scrappedautomobiles. “Fluff” is the mostly nonmetallic material recovered fromcars and trucks and includes glass, fibers, foams (especiallypolyurethane foams), and various plastics and other resins.

Before the mixed waste plastics are introduced into a reactor, they maybe shredded or otherwise reduced to a particulate state. A variety ofsize reduction means are well known in the art and any of these meanscan be employed in the process of this presently disclosed and claimedinventive concept(s). The size reduction means include, but are notlimited to, a shredder, a chopper, a grinding apparatus or combinationsthereof, which can be employed in a sequential, parallel, or tandemmanner. For example, the thermoset polymer, which may initially take theform of large articles such as automotive body panels, tires, gaskets,bushings, shower stalls, boat hulls, furniture or automotive seatcushions, or foamed insulation from appliances or building constructionor demolition, can be first subjected to a coarse shredding, chopping,or crushing operation. The coarsely shredded or chopped thermosetpolymer can subsequently be grounded, pulverized, or further crushed toyield the fine particles required.

Additional pretreatment steps can be incorporated, if desired, such asflotation, washing, drying, separation, or the like. Non-polymericmaterials such as metals, glass, wood, paper, cloth and the like areremoved from this separation process. The separation process can beaccomplished using conventional means such as a magnetic separationdevice or a classification device separating according to density suchas a shaking table or a flotation tank. The separation process can becarried out before or after the size reduction step.

In any case, it is important that the mixed waste plastics are in a formof relatively small particles when contacted with the solid catalystcomponent in the reactor in order to achieve optimum results from theprocess of this presently disclosed and claimed inventive concept(s).Small particles are desirable in order to maximize the surfacearea/volume ratio of the particles, thus increasing the rate at whichthe plastic particles will be converted in the reactor, and also toensure that the plastic particles do not rapidly “settle out” in afluidized bed reactor from the solid catalyst component (which optimallyalso is relatively small in size). The average diameter of the mixedwaste plastic particles should therefore be less than about 1 cm. In oneembodiment, the average diameter of the mixed waste plastic particles isless than about 1 mm. In another embodiment, the average diameter of themixed waste plastic particles is less than about 0.5 mm.

Example of a process of converting mixed waste plastics into lowmolecular weight organic compounds using the solid catalyst component isnow described. Referring to FIG. 1, a high level schematic diagram ofconverting mixed waste plastics into low molecular weight organiccompounds is shown.

If a mixed waste plastic contains polyvinyl chloride (PVC),polyvinylidene dichloride (PVDC) and other halogenated plastics, it willbe fed through line 1 into a thermal reactor 2. The pyrolysis of thehalogenated plastics can be performed in the reactor 2 using a two-steptemperature program under atmospheric pressure. The two-step temperatureprogram can eliminate hydrogen chloride from the reactor and theformation of chlorinated hydrocarbons in the products. Thus, thepyrolysis produces the plastics without halogenated hydrocarbons (lessthan about 15 ppm).

In the first step of the pyrolysis, the temperature is increased fromroom temperature to a temperature between about 300° C. and about 330°C. for at least about two hours. The evolved HCl is carried out from thetop of the reactor with an inert carrier gas (e.g., N₂) through line 4.In the second step, the temperature is subsequently increased to a finalpyrolysis temperature from about 400° C. to about 450° C. and kept untilthe end of the pyrolysis.

The mixed waste plastic after the pyrolysis is fed into a catalyticreactor 7 along line 3. A mixed waste plastic without PVC, PVCD andother halogenated plastics can be fed into a catalytic reactor 7 alongline 1′ directly without the pyrolysis step. The mixed waste plasticparticles may be admixed with or suspended in a hydrocarbon-basedcarrier (preferably liquid in form) such as crude oil, recycledlubricating oils, waste cooking oils, melted thermoplastic polymers, andthe like prior to introduction into the reactor. The hydrocarbon-basedcarrier will be catalytically cracked into useful volatile organiccompounds.

In certain non-limiting embodiments, the reactor 7 is a catalyticfluidized bed reactor. The mixed waste plastics particles are heatedwith the solid catalyst component particulates in the catalyticfluidized bed reactor 7 at a temperature effective to convert all orpart of the polymeric portion of the particles into a volatile organiccomponent. In general, the temperature in the catalytic fluidized bedreactor will be varied from about 450° C. to about 750° C. In oneembodiment, the temperature will be varied from about 500° C. to about700° C.

The reactor velocity must be sufficient to maintain the catalyst and thepolymer particles present in random motion. The velocity should be highenough to effectively carry over through line 8 a first streamcomprising a volatile organic component generated in the process of thispresently disclosed and claimed inventive concept(s). A carrier gas maybe introduced into the reactor 7 in order to maintain the desiredreactor velocity. The carrier gas, which may be introduced through line6, for example, can be an inert gas such as nitrogen or helium; one ormore light hydrocarbons such as methane, ethane, butanes or the like;steam or some combination or mixture thereof.

The catalyst is deployed in a fluidized bed reactor, preferably a denseor “fluffed” fluidized bed so as to minimize the distance between theplastic particles and the catalyst particles and to prevent theunconverted plastic particles from settling too rapidly to the bottom ofthe reactor, while at the same time promoting effective, rapid, andintimate mixing of the components present in the reactor. Methods andequipment for using a zeolite-type catalyst in a fluid bed reactor arewell known and are described, for example, in Venuto et al., FluidCatalytic Cracking With Zeolite Catalysts, Marcel Dekker (1979); Sterka,“Fluid Catalytic Cracking”, in Chemical and Process TechnologyEncyclopedia, Considine, Ed., McGraw-Hill (1974) pp. 505-509; andAnonymous, “Fluidized Bed Operations”, Ibid., pp. 509-511. The averageconcentration of catalyst particles within the fluidized bed reactor canbe about 5 to about 15 pounds per cubic foot. Since at least a portionof the mixed waste plastic particles are likely to be larger or heavierthan the catalyst particles, it is desirable to introduce the mixedwaste plastic particles into the reactor at a point near the top of thefluidized catalyst bed reactor.

In other non-limiting embodiments, catalytic reactor 7 may be anon-thermal catalytic plasma reactor, which may be configured as a fluidbed reactor or fixed bed reactor. The temperature and pressure in thenon-thermal catalytic plasma reactor may be lower than a catalyticreactor without plasma. For example, the temperature in the non-thermalcatalytic plasma reactor may be less than about 300° C. In suchnon-thermal catalytic plasma reactors, the waste plastic stream is firstdeconstructed via breaking the C—C and C—H bonds by the highly energeticelectrons (referred to as “hot electrons” and having 1-10 eV) generatedfrom gas discharges in a high voltage electric field. The intermediatespecies formed in the deconstruction process will adsorb on the surfaceof the catalysts in catalytic reactor 7 and convert into varioushydrocarbon products, such as, by way of example only, paraffins,olefins, and aromatic compounds, as well as combinations thereof,depending on the catalyst and reaction conditions employed.

In embodiments employing the use of a non-thermal catalytic plasmareactor, the applied electric field controls the average energy of thehot electrons and drives the formation kinetics of activatedintermediates from plastic degradation. This plasmachemical approach hasseveral unique advantages over the existing technologies, such asthermal pyrolysis, for the degradation and upcycling of waste plastics.First, plasma-derived hot electrons are highly efficient for breakingdown the chemical bonds of plastics without significant input of thermalenergy, thus allowing for much lower operating temperatures. Morespecifically, due to its non-equilibrium features, non-thermal plasmacould improve reaction activity and product selectivity by enabling somethermodynamically unfavorable reaction channels/pathways that are notattainable via conventional pyrolysis. Second, the plasmachemicalapproach also has advantages over plasma-only pyrolysis because theincorporation of highly efficient catalytic materials in the plasmareactor could selectively convert the intermediates from plasticdegradation into more valuable chemicals and fuels, thus improving theenergy efficiency and process economics. Third, the operating conditionsof the plasma-catalytic process can be precisely controlled and thereaction time with non-thermal plasma is relatively short, therebyresulting in a highly efficient, rapid, and flexible process forproducing chemicals and fuels from mixed waste plastics.

If desired, a catalyst separator 10 can be positioned such that productsexiting the reactor 7 through line 8 are treated so as to remove anycatalyst that may have been inadvertently carried over and to returnthis catalyst to the reactor. Catalyst separator 10 is suitablycomprised of one or more cyclone vessels of the type commonly employedin fluid catalytic cracking processes. In addition to separating ordisengaging the particulate catalyst from the exiting product stream, itis also desirable to operate the catalyst separator 10 so as to separateand return to the reactor 7 other particulate materials such as filleror mixed waste plastic particles which may be present. The particulatecatalyst along with other particulate materials from the separator 10 isfed into a catalyst regenerator 15 through line 14.

Treatment of filled mixed waste plastic in accordance with thispresently disclosed and claimed inventive concept(s) will generate notonly a volatile organic component but also coke (a non-volatilecarbonaceous residue having a high ratio of carbon to hydrogen), filler,and a spent catalyst.

The filler may vary from very fine to very coarse in size, dependingupon the type of filler present initially in the mixed waste plastic andthe degree of size attrition or reduction experienced during processing.The fine filler component may typically exit from the catalyst separator10 together with the volatile organic component while the coarse fillercomponent will tend to remain with the catalyst in the fluidized bedrector. Catalyst separator 10 may be configured and operated so as toachieve the desired separation of the filler component exiting reactor7.

The coke will typically be deposited on the surfaces of the spentcatalyst and the filler. The spent catalyst will be lower in activitythan the fresh catalyst. To regenerate the spent catalyst and to removethe coke from the spent catalyst and the filler so that the catalyst andfiller may be desirably reused or recycled, a second stream comprisingthe spent catalyst, coarse filler component and coke is withdrawn fromthe reactor 7 through line 9 and passed into the catalyst regenerator15, wherein the stream is heated in the presence of oxygen, or air, or amixture of oxygen and other inert gases (supplied through line 17) at atemperature effective to convert the coke to carbon dioxide and waterand to regenerate the catalyst. In one embodiment, the temperature inthe regenerator 15 is from about 450° C. to about 900° C. In anotherembodiment, the temperature in the regenerator 15 is from about 600° C.to about 750° C. An advantage of this process is that the heat generatedin the catalyst regeneration step can be used in other steps of theprocess requiring the input of heat such as the fluidized bed reactor.The overall process is thus remarkably energy efficient. Gaseousproducts are removed through line 25, while the particulate product(regenerated catalyst and filler, both of which are essentially free ofcoke) is withdrawn via line 16. The particulate product is subsequentlytreated in a separator 18 so as to fractionate the particulate producton the basis of size, weight, or density, thus separating theregenerated catalyst from a fine reclaimed filler component and a coarsereclaimed filler component. The separator 18 may suitably comprise oneor more cyclone vessels, sieves, filters, or the like. The separationmeans are chosen such that the particles present are separated on thebasis of both weight and size. The fine reclaimed filler component willcomprise that portion of the filler component (withdrawn through line26) which is smaller in size and/or lighter in weight than theregenerated catalyst (which typically will have an average particle sizeof from about 50 to about 150 microns). The coarse reclaimed fillercomponent (withdrawn through line 19) will comprise the portion of thefiller component which is larger in size and/or heavier than theregenerated catalyst. A key advantage of the process of this presentlydisclosed and claimed inventive concept(s) is that the filler which isrecovered is essentially free of any residual coke and will be in a formsuitable for immediate reuse as filler in a filled thermoset orthermoplastic resin.

The regenerated catalyst is fed back into the reactor 7 through line 20so as to replenish the supply of active catalyst in the reactor. Thecatalyst regeneration process is carried out in a continuous manner. Theregenerated catalyst will contain a minor amount of filler comprisingparticles comparable in size and weight to the catalyst particles. Thesefiller particles will not tend to accumulate, however, due to theirproclivity to gradually attrite during the physical handling steps ofthe process, which eventually will reduce the size of said particles toan extent as to permit facile separation from the catalyst particles.For this reason, the solid catalyst component particles should beselected such that they have an exceptionally high degree of resistancetowards attrition.

The volatile organic hydrocarbon component disengaged from catalystseparator 10 passes through line 11 into a product separator 12 and isseparated into the desired hydrocarbon product streams. The nature ofthese hydrocarbon product streams will vary depending upon thecomposition of the mixed waste plastic, the type of catalyst, and theoperating conditions within the reactor, among other factors.

In one particular embodiment as shown in FIG. 1, at least a portion oflights, gases and olefins 13 of the volatile organic hydrocarboncomponent is separated from the rest of the product stream 21 in theproduct separator 12. Olefins include, but are not limited to, ethene,propene, butenes, and the like. The rest of the product stream include,but are not limited to, benzene, toluene, xylene and other hydrocarbons.

Suitable methods for separating lights, gases and olefins from othervolatile organic carbon products are known to those of ordinary skill inthe art. For example, lights, gases and olefins can be separated fromother volatile organic carbon products by cooling product stream to atemperature that lies between the boiling points of the lights, gasesand olefins, and the other volatile organic hydrocarbon products.Optionally, the product separator 12 can comprise a multi-stageseparator. For example, the product separator 12 can comprise a firstseparator that directly separates the gaseous products (includingolefins) from liquid products (e.g., high boiling point aromatics suchas benzene, toluene, xylene, etc.), and a second separator thatseparates at least a portion of the olefins from other gaseous products(e.g., gaseous aromatics, CO₂, CO, etc.). The methods and/or conditionsused to perform the separation can depend upon the relative amounts andtypes of compounds present in the fluid hydrocarbon product stream, andone of ordinary skill in the art will be capable of selecting a methodand the conditions suitable to achieve a given separation given theguidance provided herein.

The portion of the lights, gases and olefins 13 are recycled back to thefeed stream after passing a compressor 22 through line 23. Recyclingolefins can increase the amount of aromatic compounds such as benzene,toluene, xylene and the like present in the product stream, relative tothe amount of aromatic compounds that would be present in the productstream in the absence of recycling but under essentially identicalconditions.

In some embodiments, co-feeding olefins to the reactor can result in anincrease in aromatic compounds in the reaction product of at least about5%, at least about 10%, or at least about 20%, relative to an amount ofaromatic compounds that would be produced in the absence of the olefinco-feed. Olefins may be reacted with hydrocarbonaceous material in anysuitable ratio. In some embodiments, the ratio of the mass of carbonwithin the hydrocarbonaceous material to the mass of carbon in theolefins in a mixture of hydrocarbonaceous material and olefins that isto be reacted is between about 2:1 and about 20:1, between about 3:1 andabout 10:1, or between about 4:1 and about 5:1.

It is, of course, not possible to describe every conceivable combinationof the components or methodologies for purpose of describing thedisclosed information, but one of ordinary skill in the art canrecognize that many further combinations and permutations of thedisclosed information are possible. Accordingly, the disclosedinformation is intended to embrace all such alternations, modificationsand variations that fall within the spirit and scope of the appendedclaims. Furthermore, to the extent that the term “includes,” “has,”“involve,” or variants thereof is used in either the detaileddescription or the claims, such term is intended to be inclusive in amanner similar to the term “comprising” as “comprising” is interpretedwhen employed as a transitional word in a claim.

All references, articles, patents, and pending patent applications citedherein are hereby expressly incorporated herein in their entireties byreference.

What is claimed is:
 1. A process, comprising (a) feeding particles of amixed waste plastic, plasma, and a solid catalyst component into anon-thermal catalytic plasma reactor, the solid catalyst componentcomprising (I) a zeolite and (ii) alloyed metals comprising at least onenoble metal alloyed with at least one transitional metal; (b) heatingthe particles of the mixed waste plastic and the solid catalystcomponent at a temperature effective to produce a coarse filler,inorganic components, coke, a volatile organic component, and a spentcatalyst component; (c) withdrawing a first stream comprising thevolatile organic component from the reactor; (d) withdrawing a secondstream comprising the spent catalyst component, the coke, the coarsefiller and the inorganic components from the reactor; (e) heating thesecond stream in a regenerator in the presence of oxygen, air, or ablend of oxygen with an inert gas at a temperature effective to convertthe coke to a mixture of carbon monoxide, carbon dioxide and water, andto regenerate the solid catalyst component; and (f) separating theregenerated solid catalyst component from the coarse filler and theinorganic components.
 2. The process of claim 1, wherein the inert gasof step (e) is nitrogen.
 3. The process of claim 1, wherein the volatileorganic component comprises a light C₂-C₆ olefinic product stream. 4.The process of claim 3, further comprising the step: (g) recycling thelight C₂-C₆ olefinic product stream back to the reactor to produce anorganic compound having a carbon backbone represented by the formulaC_(n) where n is a whole integer greater than or equal to
 6. 5. Theprocess of claim 4, wherein the organic compound is selected from thegroup consisting of benzene, toluene, xylene and combinations thereof.6. The process of claim 1, wherein hydrogen is added into the step (a).7. The process of claim 1, wherein a hydrogen source is added into thestep (a).
 8. The process of claim 1, wherein the particles of the mixedwaste plastic in step (a) have an average diameter of less than about 1cm.
 9. The process of claim 1, wherein the temperature of step (b) isless than about 300° C.
 10. The process of claim 1, wherein prior tostep (a), the particles of the mixed waste plastic are fed into athermal reactor and undergo pyrolysis.
 11. The process of claim 10,wherein the pyrolysis is performed using a two-step temperature programcomprising (I) raising the temperature to a range of from about 300° C.to about 330° C. for at least two hours; and (ii) raising thetemperature to a range of from about 400° C. to about 450° C.
 12. Theprocess of claim 11, wherein the pyrolysis produces mixed waste plastichaving less than about 15 ppm halogenated hydrocarbons.